Azo-dyestuffs insoluble in water



3,058,974 AZO-DYESTUFFS INSGLUBLE IN WATER Ulrich .Dreyer,Olfenhach-Burgel, and Werner Kirst, Ofienbach (Main), Germany, assignorsto Farbwerke Hoechst Aktiengesellschaft vormals Meister Lucius &Briin'ing, Frankfurt am Main, Germany, a corporation of Germany NoDrawing. Filed July 13, 1959, Ser. No. 826,461 Claims priority,application Germany July 18, 1958 7 Claims. (Cl. 260-147) The presentinvention relates to new aZo-dyestufis insoluble in water and to aprocess for preparing the same; more particularly it relates to complexmetal compounds of water-insoluble azo-dyestuffs corresponding to thegeneral formula on the fiber or on another substratum a diazoniumcompound of an amine of the general formula substituted by in which thebenzene nucleus a may be substituted by halogen atoms, alkyl, alkoxy,aryloxy, acyloxy, nitro, trifluoromethyl, carboxylic acid ester,carboxylic acid amide groups which may contain substituents, acyl,alkylsul'fonyl, arylsulfonyl, sulfonic acid ester, sulfonic acid amidegroups which or arylamino groups, with an arylamide of an aromatic orheterocyclic o-hydroxycarboxylic acid or acylacetic acid free fromgroups imparting solubility in water, for example sulfonic acid orcarboxylic acid groups, and treating the dyestuir' so obtained with anagent yielding metal. i

The water-insoluble azo-dyestuifs obtainable by the present inventioncan be treated after the coupling with the agents yielding metal inknown manner in substance or on the fiber. When the dyestufis areproduced on the fiber, it is, however, of advantage to add the agentsyielding metal to the dyebath and to carry out the metallization of thedyestufls during the coupling. This can be effected without difiiculty,since the diazo solutions prepared from the amines used in the processof the invention are in many cases very stable to agents yielding metaleven at high temperatures. As agents yielding metal there may be used,for example, iron, chromium, uranium, manganese, aluminum, lead, cadmiumor zinc, and preferably cobalt, copper and nickel, which may be used inthe form of their organic or inorganic salts or in the form of complexcompounds.

The new dyestuifs yield on vegetable fibers including may containsubstituents, acylamino ite res atent 3,358,974 Patented Oct. 16, 1962those of regenerated cellulose, according to the dyeing and printingprocesses known from the ice color industry, dyeings of good fastnessproperties. The green, violet, blue and blue-green dyestuifs obtainablewith the cobalt, nickel or copper compounds possess a Very good fastnessto light and are especially valuable. When a loose material, hanks or awound-up material is used, the dyestufis can be produced on vegetablefibers in a long goods-toliquorratio, while piece-goods can be dyed in acontinuous manner or according to the methods of base printing. Dyeingson piece-goods of vegetable fibers can in part be discharged to a purewhite and, furthermore, they can be reserved in known manner, forexample, with the use of phenylhydrazine-para-sulfonic acid.

The dyestuffs of this invention can also be produced on animal fibers,such as wool or silk, or on hides and furs, valuable dyeings of goodfastness properties being likewise obtained.

T=he dyestufis may also be prepared in substance and converted into thecomplex metal compounds by treating them with agents yielding metal. Themetallization is advantageously carried out inorganic solvents, such asacetone or dimethylformamide, in the presence of small quantities ofpyridine. The complex metal compounds so obtained have a greattinctorial strength. They are in general soluble in acetone, alcohol ornitrocellulose ester lacquers so that they can be used for thepreparation of colored paints. Furthermore, the complex metal compoundsprepared in substance may be used for dyeing animal fibers, such as woolor silk, or synthetic fibers, for example polyamide, polyurethane,acetyl cellulose or polyester fibers, or for coloring high molecularplastic masses.

As coupling components there may be used in the process of the inventionarylarnides of aromatic or heteroeyclic o-hydroxycarboxylic acids oracylacetic acids, for example arylamides of 2,3-hydroxynaphthoic acid orits derivatives substituted in 6-position, of2-hydroxyanthracene-3-carboxylic acid, of cresotic acids, ofhalogen-salicyclic acids, of 4-hydroxydiphenyl-3-carboxylic acid, ofZ-hydroxycarbazole-3rcarboxylic acid, of5-hydroxy-1,2,1,2-benzocarba-zole 4 carboxylic acid, of 3hydroxydiphenylene oxide-Z-carboxylic acid, of 3-hydroxydiphenylenesulfide- Z-carboxylic acid, of aceto acetic acid, of benZoyl acetic acidor terephthaloyl-bis-acetic acid.

As amino compounds which correspond to the above formula and mayadvantageously be used in the process of the invention there may bementioned, for example, 3- amino-indazol, 3-amino 4 chloro-indazol, 3amino 5- chlor'o-indazol, 3-amino 6 chloro-indazol, 3 amino 6-methylindazol, 3-amino-5-methoxyindazol, 3 amino 5-methoxy-6-chloro-indazol, 3-amino-6methoxyindazol or3-amino-6-eth0xyindazo1.

These amino compounds, only a part of which has been described in theliterature, can be prepared by known methods, for example by diazotizingo-amino-benzonitriles, reducing the diazo compounds with stannouschloride and hydrochloric acid to obtain the hydrazine compounds andcyclization in an acid medium to the S-aminoindazols. The compounds soobtained are stable and well crystallizing products which can bediazotized in known manner in a mineral acid solution. When the diazosolutions are neutralized, the diazo compounds sepa rate in the form ofdifficultly soluble, stable anhydroindazol-3-diazo-hydroxides.

The new dyestuifs are superior to the water-insoluble a'zo-dyestufisdisclosed in French Patent 981,432 and obtainable by coupling diazotized6- or 7-amino-indazol with an ary lamide of 2,3-hydroxynaphthoic acidand subsequent metallization with regard to the properties of fastness.

The following examples serve to illustrate the invention but they arenot intended to limit it thereto.

3 Example 1 Cotton yarn is treated for 30 minutes at a goods-toliquorratio of 1:20 in the following bath:

The material is then squeezed minutes in the following bath:

1.67 grams of 3-amino-5-chloro-indazol (melting at 161 to 162C.) aredissolved in 4.1 cc. of hydrochloric acid of 20 B. and a small quantityof warm water. The solution is then cooled by the addition of ice, and

4 cc. of a sodium nitrite solution of 20% strength are added. When thediazotization is complete, the bath is diluted to about 800 cc. withlukewarm water,

1.4 grams of sodium formate and 20 grams of sodium chloride, dissolvedin about 100 cc. of water, are then added and the solution is made up to1 liter with water. is rinsed and then treated for 30 minutes in a bathcontaining, per liter of Water, 3 grams of cobaltous 'cloride and 2 cc.of acetic acid of 50% strength, while raising the temperature to about90 C. During this procedure the tint turns green. The material is thensoaped at the boil with a solution containing, per liter of water, 3grams of soap and 3 grams of sodium carbonate, rinsed again and dried.

oh. and treated for 30 A full, dark green dyeing of very good fastnessto light and to wet processing is obtained.

Example 2 Cotton fabric is padded on a two-roller foulard with thefollowing solution:

13.4 grams of l-(2',3'-hydroxynaphthoylamino) benzene are dissolved in20 cc. of diglycol,

30cc. of the sodium salt of sulfonated castor oil of 50% strength and16.7 cc. of sodium hydroxide solution of 38 B. and the solution is madeup to 1 liter with Water at 90 C.

A full violet dyeing of very good fastness to light and to wetprocessing is obtained.

When, instead of 3 grams of nickel sulfate, 2 grams of copper sulfateare used for the metallization, a dark grey dyeing of very good fastnessproperties is obtained.

-2-methyl- Example 3 Cotton fabric is padded on a two-roller foulardwith the following solution:

6.48 grams of1-(2',3'-hydroxynaphthoylamino)-2,4-dimethoxy-S-chlorobenzene aredissolved in cc. of diglycol,

The claret dyeing so obtained 0 4 cc. of the sodium salt of sulfonatedcastor oil of strength and 13.2 cc. of sodium hydroxide solution of 38B. and the solution is made up to 1 liter with water at 90 C.

The dried material is developed at a goods-to-liquori ratio of 1:20 witha diazo solution which has been pre-; pared as follows: i

0.46 gram of 3-amino-6-methoxyindazol (melting at 202-5 203 C.),dissolved in 1.15 cc. of hydrochloric acid of 20 B. and a small amountof warm water, are diazotized with 1.13 cc. of a sodium nitrite solutionof 20% strength;

0.55 gram of sodium formate, i

0.5 cc. of formic acid and a solution of 2 grams of cobaltous chloridein a small amount of water i are subsequently added. The solution isthen made up 1 to 1 liter with water at 35 C.

When the material has been introduced, the temperai ture is slowlyraised to C. and after about 15 minutes to 90 C. The material is thenrinsed, soaped at the boil with a solution containing, per liter ofWater, 3 grams of soap and 3 grams of sodium carbonate, rinsed again,and

dried.

A bright green dyeing of. very good fastness to light and to Wetprocessing is obtained.

When, instead of 2 grams of cobaltous chloride, 2 grams of nickelsulfate are used in the developing bath, a violet dyeing of likewisegood fastness properties is obtained.

Example 4 Cotton fabric is padded on a two-roller foulard with a.solution containing per liter of hot water 12.8 grams of2,3-hydroxynaphthoylaminobenzene,

30 cc. of the sodium salt of sulfonated castor oil of 50% strength and19.2 cc. of sodium hydroxide solution of 38 B.

The dried fabric is printed with the following paste:

The material is then dried at about a boiling solution containing, perliter of water, 10 cc. of acetic acid of 50% strength, thoroughlyrinsed, soaped at the boil with a solution containing, per liter ofWater, 3 grams of soap and 3 grams of sodium carbonate and dried.

A green print on a white ground is obtained.

Alternatively, the fabric may be steamed neutral or acid after printingand drying, whereby the depth of the tint in increased.

strength. The

thickening of 8% C., treated with Exan'zple 5 Cotton yarn is treated ata goods-to-liquor ratio of 1:20 in the following bath:

solution of 38 B.,

5 cc. of the sodium salt of sulfonated castor oil of 50% strength and 20grams of sodium chloride.

After 30 minutes, the yarn is centrifuged and developed in the followingbath:

The material is introduced at about 60 C., a bluish red dyeing beingobtained. After a short time 2.8 grams of cobaltous chloride dissolvedin a small quantity of water are added and the temperature is slowlyraised to 90 C. The tint then turns green. After about 30 minutes, theyarn is rinsed, soaped at the boil with a solution containing, per literof water, 3 grams of soap and 3 grams of sodium carbonate, rinsed againand dried.

A medium green dyeing of very good fastness to light and to washing isobtained.

When in the above example 3.2 grams of nickel sulfate are used insteadof 2.8 grams of cobaltous chloride, a violet dyeing is obtained. Whenthe cobaltous chloride is replaced by 3 grams of copper sulfate, ablue-green dyeing is obtained. The dyeings likewise possess goodfastness properties.

Example 6 Cotton yarn is treated for 30 minutes at a goods-toliquorratio of 1:2 in the following bath:

0.9 gram of -1-(2',3-hydroxynaphthoylamino)-2-methoxy-,4-chloro-5-methylbenzene is dissolved in 1.8 cc. of denatured alcohol,

1.45 cc. of sodium hydroxide solution at 38 B.,

0.9 cc. of a formaldehyde solution of 30% strength and 0.9 cc. of hotwater and the solution is made up to 1 liter with water at 35 C.,

3 grams of the sodium salt of sulfonated castor oil of 50% strength,

6 cc. of sodium hydroxide solution of 38 B., and

20 grams of sodium chloride.

The yarn is centrifuged and developed in the following bath:

The yarn is treated for about minutes at 60 to 70 C. An aqueous solutionof 2.8 grams of cobaltous chloride is then added, the bath is heated to90 C. and the treatment is continued for about 30 minutes at thistemperature. The material is then thoroughly rinsed, aftertreated at theboil with a solution containing, per liter of water, 3 grams of soap and3 grams of sodium carbonate, rinsed again and dried.

An olive green dyeing of very good fastness to light is obtained.

When in the above example 3 grams of copper sulfate are used instead of2.8 grams of cobaltous chloride, at blue-green dyeing of very goodfastness to light is ob tained.

Example 7 Cotton yarn is treated for 30 minutes at 35 C. at agoods-to-liquor ratio of 1:20 in the following bath:

0.9 gram of 1-(2,3-hydroxynaphthoylamino)-2,5-dimethoxy-4-chlorobenzeneis dissolved in 3 cc. of denatured ethyl alcohol,

0.45 cc. of sodium hydroxide solution at 38 B.,

0.9 cc. of formaldehyde solution of 30% strength and 1 cc. of hot waterand the solution is made up to 1 liter with water at 35 C.,

3 cc. of the sodium salt of sulfonated castor oil of 50% strength,

6 cc. of sodium hydroxide solution of 38 B. and

20 grams of sodium chloride.

The yarn is centrifuged and developed in the following bath:

1.48 grams of S-amino-G-methylindazol in the form of the diazoniumcompound are dissolved with 1 gram of a reaction product of ethyleneoxide and a fat alcohol and 3.1 grams of hydrochloric acid of 20 B6. inwater at 4 grams of sodium acetate,

2.15 cc. of acetic acid of 50% strength and 20 grams of sodium chlorideare then added and the whole is made up to 1 liter with water at 60 C.

After about 15 minutes, an aqueous solution of 2.8 grams of cobaltouschloride is added, the bath is slowly heated to C. and the yarn istreated at this temperature for about 30 minutes. It is then thoroughlyrinsed, soaped at the boil with a solution containing, per liter ofwater, 3 grams of soap and 3 grams of sodium carbonate, rinsed again anddried.

An olive green dyeing of very good fastness to light and to washing isobtained.

When, in the above example, 3.5 grams of nickel sulfate are used insteadof 2.8 grams of cobaltous chloride, a violet dyeing of very goodfastness to light and to washing is obtained.

When instead of 2.8 grams of cobaltous chloride 3 grams of coppersulfate are used, a greenish grey-blue dyeing is obtained which likewisepossesses good fastness properties.

Example 8 Bleached cotton fabric is padded on the foulard with thefollowing solution and then dried:

6.7 grams of l-(2,3'-hydroxynapththoylamino)-2-methylbenzene aredissolved, in the hot, with 30 cc. of the sodium salt of sulfonatedcastor oil of 50% strength and 12.8 cc. of sodium hydroxide solution of38 B. and

the solution is made upto 1 liter with water.

The fabric is then printed with a paste containing, per kilogram,

70 grams of the sodium salt of phenylhydrazine-parasulfonic acid,

50 grams of sodium hydroxide solution of 38 Be,

380 grams of water and 500 grams of starch tragacanth thickening.

The fabric is then dried and developed at 70 C. in the following bath:

4.35 grams of 3-amino-6-rnethoxyindazol in the form of the diazoniumcompound are dissolved in a hot aqueous solution of 2 grams of areaction product of ethylene oxide and a fat alcohol and 7.2 cc. ofhydrochloric acid of 20 B. and mixed with 20 cc. of acetic acid of 50%strength and an aqueous solution of 20 grams of sodium acetate and 6.6grams of cobaltous chloride. The solution is then made up to 1 literwith Water at 70 C.

After an air-passage of about 1 minute, the material is treated forabout seconds in a bath at 90 C. containing, per liter of water, 10 cc.of acetic acid of 50% strength, rinsed, soaped with a solutioncontaining, per liter of water, 1 gram of a condensation product from anamino-alkyl-sulfonic acid and a high molecular fatty acid, andfurthermore 3 grams of sodium carbonate, rinsed again and dried.

A white resist on a green ground is obtained.

Example 9 Mixed yarn of Wool and staple fiber of regenerated cellulose(50:50) is treated for 45 minutes at 55 C. at a goods-to-liquor ratio of1:30 in the following bath:

The material is then rinsed with a solution containing, per liter ofwater, 30 grams of sodium chloride and 1 gram of sodium carbonate and,after dripping off, developed in the following solution:

0.74 gram of 3-amino-6-methoxyindazol in the form of the diazoniumcompound is dissolved at 70 C. in an aqueous solution of 1 gram of areaction a fat alcohol and 1.7 cc. of hydrochloric acid of B.

2 cc. of acetic acid of 50% strength,

10 grams of sodium acetate and 3 grams of cobaltous chloride are thenadded and the bath is made up to 1 liter with water at 70 C.

When the yarn is introduced, the bath is slowly heated to 90 C. and thematerial is treated for minutes at this temperature. It is then rinsed,treated for 20 minutes at 60 C. with a solution containing, per liter ofwater, 1 gram of a reaction product from ethylene oxide and an alkylphenol and 1 gram of the sodium salt of nitrilotriacetic acid, rinsedagain and dried.

A green tone-in-tone dyeing is obtained.

When, instead of 0.74 gram of 3-arnino-6-methoxyindazol, 0.7 gram of3-amino-6-chloro-indazol, likewise in the form of the diazoniumcompound, is used, an olive green dyeing is obtained.

When natural silk is used instead of the mixed yarn of wool and staplefiber of regenerated cellulose, an olive green dyeing is likewiseobtained.

product from ethylene oxide and Example 10 Cotton yarn is treated forminutes at 35 C. at a goods-to-liquor ratio of 1:20 in the followingbath:

The yarn is centrifuged and developed at a goods-toliquor ratio of 1:20with a diazo solution which has been prepared as follows:

0.55 gram of 3-amino-6-rnethoxyindazol and 0.55 gram of cobaltouschloride are dissolved with 1 cc. of a reaction product of ethyleneoxide and a fat alcohol, 1

1.36 cc. of hydrochloric acid of 20 B. and

15 cc. of water.

0.14 cc. of a sodium nitrite solution of 10% then added anddiazotization is carried minutes.

3 cc. of acetic acid of 50% strength,

10 grams of sodium acetate,

1 gram of potassium bichromate and 20 grams of sodium chloride are thenadded and the solution is made up to 1 liter with water at 50 C.

When the material is introduced, the bath is heated to 1 C. and thematerial is treated at this temperature for l 30 minutes. It is thenrinsed, soaped at the boil with l a solution containing, per liter ofwater, 3 grams of soap 1 strength isl out for 30\ and 3 grams of sodiumcarbonate, rinsed again and dried.

A yellowish green of good fastness properties is obtained.

Example 11 Cotton yarn is treated for 30 minutes at 35 C. at agoods-to-liquor ratio of 1:20 in the following bath:

0.98 gram of 1-(2'-hydroxycarbazole-3-carboylamino)- 4-chlorobenzene isdissolved in 3 cc. of denatured ethyl alcohol,

0.5 cc. of sodium hydroxide solution of 38 B. and

6 cc. of Warm water and the solution is made up to 1 liter with water at35 C.,

3 grams of a condensation product from high molecular fatty acids andprotein degradation products and 10 grams of sodium hydroxide solutionof 38 B.

The yarn is centrifuged and treated in the following bath:

The material is treated for 15 minutes at 40 C., the bath is then heatedto 90 C. and the material is treated for 30 minutes at this temperature.It is then thoroughly rinsed, soaped at the boil with a solutioncontaining, per liter of water, 3 grams of soap and 3 grams of sodiumcarbonate, rinsed again and dried.

A full blue-violet dyeing of very good fastness properties is obtained.

product of ethylene oxide and a strength.

Example 12 36 parts by weight of 1-(2',3-hydroxynaphthoylamino)-2,4-dimethoxy-5-chlorobenzene are made into a paste with 0.5 part byweight of a reaction product of about 20 mols of ethylene oxide and 1mol of oleyl alcohol and 36 parts by volume of sodium hydroxide solutionof 38 B. and the paste is heated for 15 minutes. 1000 parts by volume ofhot water are then poured over the paste which is dissolved by boiling.The solution so obtained in run, while stirring well, into a diazosolution which has been prepared by diazotizing in the usual manner 16.3parts by weight of 3-amino-6-methoxyindazol. The temperature of thereaction solution is kept at 25 to 3 C. by cooling. When the coupling iscomplete, the red dyestuff which has formed is suction-filtered andwashed.

For the conversion of the dyestulf into the complex copper compound, themoist filter cake is suspended in 1000 parts by volume of acetone andmixed with a concentrated aqueous solution of 17.1 parts by weight ofcrystalline cupric chloride and 25 partsby volume of pyridine. Afterstirring for a short time, metallization is complete. The reactionmassis diluted with water to about 3000 parts by volume and acidifiedwith 50 parts by volume of hydrochloric acid of 20 B. The dyestuif soobtained is suction-filtered, washed and dried. It is a bluish blackpowder which in admixture with a white pigment yields grey-blue tintswhen used for a linseed oil paint.

When in the above example 24 parts by weight of crystalline cobaltouschloride are used instead of 17.1 parts ofv Weight of cupric chlorideandthe metallization is conducted for hours at room temperature, whilestirring, the complex cobalt compound is obtained in the form of agreenish black powder which in admixture with a white pigment yieldsgreen tints when used for a linseed oil paint.

For the preparation of the complex nickel compound the cupric chlorideis replaced in the above example by 24 parts by weight of crystallinenickel chloride and the metallization is carried out by stirring for 5hours and heating under reflux. A dark powder is obtained whichdissolves in organic solvents to give a violet solution. It is suitablefor the preparation of lacquers and varnishes and for coloring highmolecular plastic masses or for dyeing synthetic fibers.

Example 13 v U Cotton fabric is padded on the foulard with the followingsolution and dried:

6 grams of 1-(2',3-hydroxynaphthoylamino)-2,4-dimethoxy-S-chlorobenzeneare dissolved in cc. of denatured ethyl alcohol,

20 grams of Monopol Brilliant Oil and 10 cc. of sodium hydroxidesolution of 38 B. and the solution so'obtained is made up to 1 literwith hot water at 90 C.

solution;

2.8 grams of 3-amino-4-chloro-indazol, dissolved in 13.7 cc. ofhydrochloric acid of 20 B and 60 cc. of water, are introduced into asolution of 1.34 grams of sodium nitrite in 20 grams of ice water.

the addition of h 20 grams of sodium acetate.

After passing air through the material for about 30 seconds, thematerial is treated with water at 80 C., rinsed, soaped at 60 driedmaterial is printed with the following printing paste:

200 grams of sodium-formaldehyde-sulfoxylate,

50 grams of the sodium salt of benzylsulfanilic acid 1:1, 100 grams ofpotassium carbonate, 30 grams of anthraquinone paste of 30% strength,350 grams of starch-tragacanth thickening, 270 grams of water 1000grams.

The material is then dried, steamed for 7 minutes,

rinsed at 80 10 grams of sodium rinsed again and dried.

When the diazotization is cornplete, the whole is made up to 1 literwith water after i C., rinsed again and dried. The" 1 gram of coppersulfate and gram of a reaction product from about'10 mols of ethyleneoxide and 1 mol of isododecyl phenol, 3 grams of sodium carbonate, 1.2grams of cobaltous chloride and 2.5 grams of aminoacetic acid, a greendyeing with white discharge effects is obtained.

By the additional use of vat dyestuffs inthe discharge printing paste,colored effects on blue-grey or green ground can furthermore beprepared.

Example 14 Chrome-tanned and pre-soaked white lambskins are treated inthe proportion of dry weight to dyebath of 1:20 for 90 minutes at 3840C. in the following bath;

0.5 gram of 1 (2,3 hydroxynaphthoylamino)-2,4-dimethoxy-S-chlorobenzeneis dissolved in 1.5 cc. of denatured ethyl alcohol,

0.17 cc. of sodium hydroxide solution of 32% strength,

0.5 cc. of formaldehyde solution of 30Z strength and 0.5 cc. of water,and the solution so obtained is introduced into a bath containing, perliter of water,

3 grams of a condensation product from fatty acids of high molecularweight and protein degradation products,

5 cc. of a formaldehyde solution of 30% strength,

10 cc. of sodium hydroxide solution of 32% strength and 100 grams ofsodium chloride.

' The skins are then treated for 10 minutes in a solution containing,per liter of water,

grams of sodium chloride, 2 grams of sodium bicarbonate and 2 grams ofsodium carbonate.

in the usual manner, 0.2 gram of a reaction product from .40 Thedyestufl? is then developed on a three-roller foulard .by dipping thematerial twice into the following disazoabout 20 mols of ethylene oxideand 1 mol of octode'cyl alcohol, 20 grams of sodium chloride, 4 cc. ofacetic acid of 50% strength and 10 grams of sodium acetate.

After about 1 hour, 4 grams of copper sulfate dis- -1 solved in waterare added to. this bath. It is'then heated .to 65 C. and the material istreated for 2 to 3 hours at this temperature. The skins are then laidfor 1 hour into a bath at 30 C. containing, per liter of water, 3 cc.

30f formic acid of 85% strength and 1 gram of sulfuric acid of 96%strength, and rinsed cold. 'Iheflesh side -of the skins is then brushedwith a sodium chloride solution, fat-liquored, dried and cleared. A greydyeing of very good fastness to light is obtained.

Example 15 1 kilogram of cotton yarn is treated for 45 minutes at 35 C.in the following bath:

' 25 grams of 1 (-2,3'hydroxynaphthoylamino)-2,4-dimethoxy-S-chlorobenzene are dissolved in 75cc. of denatured ethyl alcohol,

white discharge eflt'ects is ob- 8.4 cc. of sodium hydroxide solution of38 B.,

8.4 cc. of a formaldehyde solution of 30% strength and 25 cc. of hotwater, and the solution so obtained is made up to 20 liters with waterat 35 C., 7 v

120 cc. of sodium hydroxide solution of 38 B.,

grams of Monopol Brilliant Oil and 400 grams of sodium chloride.

The material is then centrifuged'and developed in the following bath:

14 grams of 3-amino-6-trifluoromethyl indazol and 25 grams of colbaltouschloride are dissolved in 240 cc. of water and 54.5 cc. of hydrochloricacid of 20 'B., and the solution so obtained is diazotized by stirringit into a solution of 1 1 5.32 grams of sodium nitrite in 200 cc. of icewater.

The diazo solution so obtained is introduced into a bath containing, per20 liters of water at 35 C. to 40 C 20 cc. of acetic acid of 50%strength, 5

grams of potassium bichromate, 200 grams of sodium acetate and 400 gramsof sodium chloride.

The diazo solution so obtained is made up to liters with water When thematerial has been introduced at C., the 10 bath is slowly heated to 90to 95 C., and the material is treated for 30 minutes at thistemperature. It is then rinsed hot and cold, soaped at the boil with awashing agent in a solution containing, per liter of water, 1 gram ofthe sodium salt of ethylenediamine-tetra-acetic acid 1 and 1 gram ofsodium carbonate, rinsed again hot and cold, and dried.

A bluish green dyeing of very good properties of fastness is obtained.

When in the above example 11.85 grams of 3-amino- 0 S-nitro-indazol areused, instead of 14 grams of 3-aminofi-trifluoromethyl-indazol ayellowish green dyeing is obtained. a

200 grams of sodium acetate and 20 cc. acetic acid of strength, 400grams of sodium chloride. l

The material is then rinsed and minutes at C. to 20 liters of water,

after-treated for 30 C. in a solution containing, per

Example 16 1 kilogram of cotton yarn is treated for 45 minutes at 25 35C. in the following bath: 20 grams of2-(2,3'-hydroxynaphthoylamino)-naphthalene are dissolved in 40 cc. ofdenatured ethyl alcohol, 8 cc. of sodium hydroxide solution of 38 B.,

A blue-grey dyeing of very good properties of fastness is obtained.

When in the above example 36 grams of cobaltous chloride and 72 grams ofaminoacetic acid are used for the metallization instead of 30 grams ofcopper sulfate and 90 grams of triethanolamine, and the material is 30treated as indicated above, a green dyeing of very good fastness tolight and washing is obtained. 20 cc. of a formaldehyde solution of 30%strength and The following table indicates a number of further com- 20cc. of hot water and the solution so obtained is made pounds which canbe used in this invention, and also the up to 20 liters with water at 35C., tints of the azo-dyestuifs produced from these components 200 cc. ofsodium hydroxide solution of 38 B. and

35 on the fiber, which likewise possess good properties of grams ofMonopol Brilliant Q11. fastness.

Tint Diazo component Coupling component Cobalt complex Nickel complexCopper complex 1- (2,3 -hydroxynaphthoylamino) -2-methyl- Bluish greenen ne Blye-grey.

1-(2,3'-hydroxynaphthoylamino)-2-methyl-4- do Violet Do.

chlorobenzene.

1-(2,3-hydroxy-naphthoylamino)Janethoxydo Blue-green.

4chloro5-n1ethylbenzene.

2-(2,3-hydroxynaphthoylamino)-naphthalene Green-grey Bluish claret Do.1-(6-bromo2,3-hydroxy-naphthoylamiuo)-2- Green Reddish dark blue Do.

methoxy-benzene.

1-(2-hydroxy-carbazo1e'3-earboylamino)-4- Violet-brown Violet.-

chlorobenzene.

Grcenish dark grey.

Dark grey.

Dark red-brown Greenish dark grey.

-d0- Do. diphenylene oxide. 1-g,3-hydroxy-naphthoylamlno)-2-methoxy-Olive green Dullred-vlolet Blue-grey.

enzene. 1-(2,3-hydroxy-naphthoylamino)-2-methyl- Brownish green ClaretReddish grey.

4-chlorobenzene. 2-2',3'-hydroxy-naphthoylamino)-naphtha- Olive green.Currant Blue-grey.

ene. 3-amino-6-chlorindazol l-(2;3-hydroxy-naphthoylamino)-2,4-din1eth-B1uishgree11- .do Do.

oxy-E-chlorobenzene. 1-(6-brom0-2,3-hydroxy-naphthoylamtno)-2- .d0Bluish violet Blue green.

methoxybenzene. 1-gtfi-hydroxy-naphthoylamino)-2-metl1yl- GreenBlue-grey.

enzene. 1(2,3'-hydroxy-naphthoylamino)-2-methyl-4- do Do.

methoxybenzene. 1-(2,3-hydroxy-naphthoylamino)-2,5-dimeth- ...do Do.

oxybenzene. 1-(2,3hydroxy-naphthoylamino)-2-methoxy- -d0 D0.

5-chlorobenzene. 1-(2',3-hydroxy-naphthoylamino)-2,6dimeth- Do.

oxy-et-chlorobenzene. 1-g2,3-hydroxy-naphthoylamlno)-naphtha- Do.

ene. 1-(2-lt1fi'dirgxy-anthracenc-3'-earboylamino)-2- Green.

me y enzene. 3-amino-6-methylindazol... 2,3-hydroxynaphthoylaminobenzeneCurrant Greem'shgrey-blue.

Do 1-12,3-hydroxynaphthoylamino) -2-methy1- Violet Do.

enzene. Do 1-2,3-hydroxynaphthoylamino)-2-methoxy- Bluish claret Do.

enzene. Do 1-(2,3-hydroxynaphthoy1an1i.no)2,4-dimethdo Violet. Do.

oxy-fi-chlorobenzene.

l e Tint Dlazo component Coupling component e Cobalt complex Nickelcomplex Copper complex 3-emino-6-methy1ind z01.. 1-%{'Jgdroxmaphthoylamino)-2-rnethyl-4- Olive green Bluish claret Greenishgrey-blue,

o oro enzene. 1-(2',3-hydroxynaphthoylamino)-2-meth0 Y- Violet Do.4-ehloto-5-methylbenzene. 2-1(2,3 -hydroxynaphthoylamino) -naphtha.- findo Do.

0119. 1-(2-hYdroxy-carbaz0le-3-carboylamlno)-4- Dark grey Dark violetReddish dark blue chlorobenzene. 1- (6-bromo:2,3-hydroxynaphthoylamino)-2- Bright green Reddlsh dark blue methoxybenzene. 4,4 -bis- (2" ,3"-hydroxynaphthoylamino) -3,3' Gr Curra dimethoxy-dlphenyl.l-(2-hydroxya11thrnceno-3-carboy1amino)-2- Yellowish green Greenmethylbenzene. 1 -hydroxy-1,1,2,2- benzocarbazole4- Dark brown Darkgrey-.. carboylammo)-4-methoxybenzene.Terephthaloyl-bls-(l-acetylamino-2methoxy- Yellow of an olive hue..."Old gold 4-ehloro-5'methylbenzene) V1-(2'hydroxy-carbazole-3-carboylamlno)-41 Dark grey Currant-.chlorobenzene. 1-(2',3-hydroxynaphthoylamino)-2,4-dimeth- Brlght greenViolet ylbenzene. r 1- (2,8 -hydroxynaphthoylamlno) -2-methyl- Gr dobenzene. I 1-(2,3-hydroxynaphthoylamlno) -2-methyl-4- Yellowish green(in chlorobenzene. 1-(2,3-hydroxynaphthoylamino)-2-methyl-5- r dochlorobenzene. 1-(2,3-hydroxynaphthoylamino) -2-methoxy- Y ellowlsh gren do 4-chloro-5-1nethylbenzene.1-(2,3-hydroxynaphthoylamlno)-2,5-dlmeth --.d fi

oxybenzene. 1- (2 3-hydroxynaphthoylamlno)-2-methoxydo 5-c orobenzene.1-1(2,3'-hydroxynaphthoylemino) -naphtha- -----d0, d0 ene. 1- 12,3-hydroxyna.ph thoylemlno)-4-ethoxy- ----d0 Red-brown enzene. 1 (2',3hydroxynaphthoylemino) 4 1 do methylbenzene. h (2,3'hydroxynaphthoylamino) 2,3 "-0 dlmethylbenzene. I Do 1 hydroxy 4methylbenzene 2 carboxylie Olive green Violet grey Greenlsh grey.

acid-phenylamide. 1 Do 1 -hydroxy 4,5 dichlorobenzene 2-carboxyl-Green-grey Red-brown Grey-green,

1c acid-phenylamide. v Do 1 (2',3 hydroxynaphthoylazm'no) 2,5Yel10WiShgreen Violet dlmethoxy--chlorobenzene. I Do 1- (4-hydroxy-diphenyl-3-carboylumino)- Ohve green Green-grey Green-grey.

2-methoxybenzene. 1 3-amino-6-ethoxylndazol l-(2,3'-hydroxynapth0y1amino)-2-meth- Yellowlsh green Reddish violet Blue-grey.

(melting at 222 to 224C). oxy-o-chlorobenzene.

Do 1- (2',3'-hydroxynaphthoylanfino) -2-methy1 Gr Violet benzene. Do 1(2',3' hydroxynaphthoylamino) 2 n methoxybenzene. Do 1 (2,3'hydroxynaphthoylamlno) 2 7 -.do -do methyl4-chlorobenzene. Do 1 (2,3hydroxynaphthoylamlno) 2 fl methyli-methoxybenzene. Do 1 (2,3'hydroxynaphthoylamlno) 2,5

dimethoxybonzene. v B-amino-G-ethoxyindazoL 1 (2,3' hydroxynphthoylamlno) 2,5 do do dimethoxy-kchlorobenzene. Do 1 (2,3hydroxynaphthoylemino) 2,4 Yellowish green "do Do. dimethoxy-S-chlorobenzene. Do 1- (2,3 -hydroxynaphth0ylamln0) -2 -meth- Gr on oxyichloro-fi-methylbenzene. Do l-l(2,3 -hydroxynephthoylamino) -naphtha-.-.d0 -.do

ene. 7 Do 1-(6-bromo-2',3hydr0xynaphthoylamino)' Yellowish green Vroletblueuu Blue-green.

2-methoxybenzene. 7 Do 2 -h(21',3 hydroxy nephthoylarnino) -neph- Green"Violet-grey..- Blue-grey.

t a one. Do 1 (2 hydroxycarbazole 3 carboylamino) 7 Greenish greyCurrant 4-chlorobenzene. Do 1 -hyd.roxy 4 methylbenzene 2 carboxylloOlive green Violet-grey Grey. aoid-phenylamlde. Do 1-hydroxy4,5-dichlorobenzene-2-carboxyl Grey Do. I 1c acld-phenylamlde. Do 1(4-hydroxy-diphenyl-3-carboy1emlno)- OhVe green Blue-green Greenishgrey.

2-methoxybenzene. 7

' Iron Zinc Uranium Cadmium complex complex complex complex 3 amino 6methoxy 1 (2',8 -hydr'oxynaphth0yla1nino) -2 -meth- Currant Violet-..Red-violet Violet,

indazol. oxy-l-chloro-t-methylbenzene.

Cobalt complex Copper complex v,

3-emino'4-chlorolndazol- 2,B-hydroxynephthylamlnobenzene Do 1 (2', 3'hydroxynaphthoylamlno) 2 methyl benzene. Do 1 (2, 3hydroxynaphthoylamlno) 2 mothoxybenzene. Do 1 (2', 3 hydroxynaphthoylamlno) 2 ethoxybenzene. Do 1 (2 3' hydroxynaphthoylamlno) 4metlloxybenzene.

Dlazo component Coupling component Cobalt complex Copper complex3-amlno-4-chloroindazol. 1 (2, 3' hydroxy naphthoylamino) 2 Greenmethyl-i-methoxybenzene. D0 1 (2, 3 hydroxy naphthoylamlno) 2, 5 d0dimethoxybenzene. D0 1 (2, 3 hydroxy --naphthoylamlno) 4 ..d0

ethoxybenzene. D0 1 (2, 3 hydroxy -'naphthoylamino) 3 Blue-greennltrobenzene. D0 1 (2, 3 hydroxy naphthoylamlno) 2 Green Blue-grey.

methyli-chlorobenzene. D0 1 3 hydroxy naphthoylamino) 2 -do D0.

methoxy-5-ehlorobenzene. 7 D0 1 -t(2i 3 -hydroxy naphthoylamino) -naphd0 Do.

a ene. D0 1 (6 bromo 2, 3 hydroxynaphthoyl .-.d0

amino)-2-n1ethoxybenzene. D 1 (2, 3 hydroxy -'naphthoylamino) 4 .dO

chlorobenzene. O 1 (2', 3 hydroxy -naphthoylan'1ino) 2, 5 d0dimethoxyA-chlorobenzcne. Do 1 -tl2i'3-hyd roxy-naphthoylamino) naph....d0 Greenlsh blue-grey.

a ene. D0 1 (2', 3 hydroxy -naphthoylan1ino) 2 d0 Blue-grey.

methoxy-4-eh1oro-5-methylbenzene. D0. 2 (2', 3 hydroxy naphthoylamino) 30 methoxydiphenylene-oxide. Do 1 2', 3' hydroxy naphthoylamino) 2, 4 dodlmenthylbenzene. D0 1 (2, 3 hydroxy naphthoylamino) 2 lue-greemethyI-Bchlorobenzene. D0 1 (2, 3 hydroxy naphthoylamino) 4 Greenmethylbenzene. 0 1 (2', 3' hydroxy naphthoylamlno) 2, 3 0

dimethylbenzene. 0 4, 4 -bis 3" hydroxynaphthoyl ami l eno-3,3-di1nethoxydiphenyl. 0 1- (2'-hydroxycarbazole -'3 carboylamino)Blue-grey 4-ehlorobenzene. 0 1 (2' hydroxy anthraeene 3 carboyl e low sg e amino) 2 -methylbenzene. D0 1 (5 hydroxy 1', 2, 1", 2-benzocarbazoleO B O 4'-earboylan1ina)-4-methoxybenzene. Do 1- (5'-hydroxy-1.2,1,2benzoearbazole Curr t carboylamino) 2 methyl 4 -methoxyenzene. 3-amm -5-methoxyindazoL- 2,3-hydroxynaphthoyl-amlnobenzeneOhve-green D0.

D0 1-(g,3-hydroxy-na,phth0y1amino)-2-methyl- Red ish blue-grey.

enzene. D0 1-(2,3'-hydroxy-naphthoy1am1n0) -2-meth- Greenlsh blue-grey.

oxybenzene. 7 D0 1 (2 3-hydr0xy-naphth0ylamin0) -2-etl1- Blue-grey.

oxybenzene. D0 1-(2,3-hydroxy-naphthoylamino) -4-meth- O.

oxybenzene. D 1-(2,3-hyd roxy-naphthoylamino)-2-methyl Re dishblue-grey.

4-methoxybonzene. o 1- (2,3-hydroxy-naphth0ylamjn0) -2,5-di- Blue-grey.

dimethoxy benzene. V 7 D0 1- t()2,3'-l1ydroxy-1 1aphtheylamino)-4-ethoxy- D0.

enzene. Do 1-2',3-hyd1oxy-naphthoy1amin0)-3-nitro- Bl is liv g e Do.

enzene. D0 1-(2,3-hydroxy-naphthoy1a.min0)-2-methylli green Violet-grey.

4-ehlorobenzene. Do 1-(2,3-hydroxy-naphthoylamin0)-2-meth- Greenishblue-grey.

oxy-5-chlorobenzene. D0 1-(2,3-hydroxy-naphthoylamino)-2,4-dimeth-Blue-grey.

0xy-5-chlor0benzene. D0 1-1(2,8-hydroxy-naphthoylamino)-naphtha Do.

ene. D0 1-(e bromo-2',3-l1yd1-oxynaphthoyl-amino- 0 Greenish blue-grey.

2-methoxy-benzene. D0 1- (2,3-hydroxy-napht;hoylarnino) -4-chlo- .-.dBlue-grey.

robenzene. D0 1-(2,3-hydroxy naphthoylamino)-2,5-dimeth- D0.

oxy-4-chlorobenzene. D0 2- 1(2,3-hydroxy-nephthoylamino)maphtha- .d0Greenish blue-grey.

ene. D0 1-(2,3 -hydroxy-naphthoylamino)-2n1el;h- 1d0 Do.

oxy-4-ehloro-5-methylbenzene. D0 l-(2,3-hydroxy-naphthoylamino)-2-methy1- Blllish Olive green Blue-grey.

5-chlorobenzene. Do 2-(2,3'-hydmxy-naphthoylamino)-3-meth- Yellowlshohve green Greenish blue-grey.

oxydjphenylene oxide. Do 1-(2'-hydroxy-carbazole-3-carboylammo)-4- GreyReddlsh dark blue.

chlorobenzene Do 1-(2'- hydr0xyanthracene-3-0arb0y1amin0)- Yellowlshgreen Green.

2-methylbenzene. Do 1 5 -hydroxy 1,2,1,2 benzocarbazole- 4- BrownViolet-grey.

carboylamino) 4 methoxybenzene. Do 1-(5'-hydroxy-1,2,1,2-benzocarbazole-4- .d0 Do,

carboylarnino)-2-methyl-i-methoxybenzene. Do 1 (2',3- hydroxynaphthoylamino) 2,4- Bluish olive green Blue-grey.

dimethylbenzene. a amino 5 methoxy 6- 2 (2,3 hydroxy naphthoy1am1no)naph- Blue-green Do.

chlorindazol. thalene.

Do 1 (2,3 hydroxy naphthoylammo) 2,4- Green D dlmeth0xy-5-chl0robenzene.D0 1 (23 -hydrnxynaphthoylam no) 2 Olive-green Do.

metfloxy-5-ehlorobenzene. D0 1 -t}2'1,3 -hydroxy -naphthoyla1m'n0)-naph- Green Do.

21 ene. Do 1 (2',3' hydroxy naphthoylamino) V2 Blue-green Do.

methoxy 4 chloro 5 methylbenzene. Do 1 (6 bromo 2 3 hydroxynaphthoylGreen D0.

amlno)-2-methoxyl)enzene. Do 1- (2'-hydroxy-carbazole -3-earboylamino)Grey Da k blu -ehlorobenzene. 3.ammg fi mgj;hyl-indazol 1 (2',3' hydroxynaphthoylamlno) 2 Green Reddish blue-grey.

ethoxybenzene.

Diazo component Coupling component 7 Copper complex Cobalt complexNickel complex 3 min indaz l 6 car 1 (2',3' hydroxynaphthoylamino) 2-4di- Blue-grey Green D1111 violet.

boxyllc acid-amide. methoxy-Schlorobenzene.

D 1-1(2,3- hydroxynaphthoylamino) -naphthado fin ene. I Do 1 (6 bromo2',3' hydroxynaphthoyl do do Do,

amino)-2-methoxybenzene. Do 1-(2,3' -hydroxynaphthoylamino) -4-ch1orodndo Do.

benzene. Do-. 1 (2,3 hydroxynaphthoylamino) 2,5 di- (In in Dmethoxy-e-chlorobenzene. Do. 2-}(223'-hydroxynaphthoylamino) -naphthadndo Do.

ene. D0 1 (2,3-- hydroxynaphthoylamlno) -2-naphrin fln thoylamino) 2methoxy 4 chloro 5 methylbenzene. D0 1 (2',3 -hydroxynaphthoylamlno)-2-methfln fin D yl-dchlorobenzene. Do 2- (2,3 hydroxynaphthoylamlno) 3mefln do Do,

thoxy-diphenylene oxide. Do 1 (2 hydroxycarbazole 3 carboylamlno)-Reddish dark brown Grey Do. .i

4-chlorobenzene. Do 1-(Z-hydroxyanthraeene-3-carboylamino)-2 GreenYellowish green"-.- Dark green.

methylbenzene. Do 1-(6 methoxy-2,3'-hydroxynaphthoylamlno)- Blue-gr nfln Greenish blue-grey,

. 2-methoxybenzene. Do 1-(6-methoxy-2,3'hydroxynaphthoylamino)- n fln.Do.

. 2-methy1-5chlorobenzene. Do 1-(%3-hydroxynaphthoylamino)-2,4-dimeth-Grey- Gr en Violet-grey.

y enzene. 1-(2,3-hydroxynaphthoylamino) -2-3-dirnethdo dn D ylbenzene.3-amino5-methylsulfonyl- 2-(2, 3-hydroxynaphthoylamino)-naphthoyl-Greenish blue-grey do Dark violet.

indazol. amJno)-naphthalene.

Do 1-1(2',3-hydroxynaphthoylamlno) -naphtha- Blue-grey do Do.

ene. Do 1-(2,3-hydroxynaphthoylamino)-2-methyl-4- Greenish blue-grey doViolet-grey,

chloro benzene. Do 1-(2',3' -hydroxynaphthoy1amino) -2,5-dimed Darkviolet,

thoxybenzene. Do 1-(2,3-hydroxynaphthoylamino)-2,4-dime- -..dod Do.

thoxy-5-chlorobenzene. Do 1-(2-hydroxycarbazo1e-3'-carboylamino) -4-Weak grey Grey Do.

ehlorobenzene. Do 1- (2'-hydroxyanthracene-3'-earboylamino)-2- Gr nYellow-gr n Olive-grey.

methyl-benzenev Do 1-(6'-bromo-2',3-hydroxynaphthoy1amino)-2- Greenlshblue-green Green Dark violet,

methoxy-benzene. s-glrginol-mbenzoylamino-2-1(2,3'-hydroxynaphthoylamlno)-naphtha- Reddlsh grey Bluish olivegreen.-- Do.

azo ene. Do 1-1(2',3-hydroxynaphthoylamino)-naphthado do Dull violet.

ene. 1-(2,3-hydroxynaphthoylamino)-2-n1ethyl-4- do Do.

chlorobenzene. 1-(2,3-hydroxynaphthoylamlno)-2,4-dime- Greenishblue-grey .-do Do.

thoxy-5-ohlorobenzene. 1-(2 ,3'-hydroxynaphthoylamino)-2,5-d1med d Do.

thoxy-benzene. 1-(2-hydroxyearbazole-3-carboylammo) -4- Violet-greyGrey" Dark violet.

chlorobenzene. 1-(2'-hyd.roxyenthracene-3'-carboylammo)-2 Yellow-Ashgreen Yellow olive green Green-grey.

methyloenzene. 1-(6-bromo-2,3'-hydroxynaphthoylamino)-2- Greenlshblue-grey Bluish olive green-.- Dull bluish-violet.

methoxybenzene.

We claim: 2. The complex metal compounds as clalmed 1n claim 1 1. Thecomplex metal compounds selected from the wherein R represents anarylamlde of the benzene, naphgroup consisting of cobalt, copper andnickel compounds thalene, diphenyl, and diphenylene oxide series of 2,3-of water-insoluble azo-dyestufis of the following generalhydroxynaphthoic acid. fo mul 3. The complex cobalt compound of theazo-dyestufi Y of the following formula l NH-N N on wherein X representsa member selected from the group consisting of hydrogen, chlorine,trifluoromethyl, nitro, methyl, methoxy, ethoxy, sulfonic aciddiethylamide, carboxylic acid amide, methylsulfonyl and benzoylarnino, Yrepresents a member selected from the group consisting 4 The com 16xcobal o of hydrogen and methoxy, and R represents a member 5 of the f uh-f; formula: c mpound of the am dyestuff selected from the groupconsisting of an arylamide of the benzene, naphthalene, diphenyl anddiphenylene oxide 01 series of 2,3-hydroxynaphthoic acid,6-bromo-2,3-hydroxynaphthoic acid, 6-methoXy-2,3-hydroxynaphthoic acid,1-hydroxy-4-methylbenzene-Z-carboxylic acid, l-hydroxyl4,5-dichlorobenzene-Z-carboxylic acid, 4-hydroxydiphenyl- JL CH3-carboxylic acid, 2-hydroxyanthracene-3-carboxylic acid, 12-hydroxycarbazole-3-carboxylic acid, 5hydroxy-1,2,1',2'- G0 NH o1benzocarbazole-4-carboxylic acid and terephthaloyl-bisacetic acid. 0H8

23 24 5. The complex cobalt compound of the azo-dyestufi of thefollowing formula of the following formula 5 01 ON=N H t I NH-N 1 NH---OH 01 10 o O-NH I OCH: 6. The complex cobalt compound of theazo-dyestufi p of the following formula 15 01 References Cited in thefile of this patent UNITED STATES PATENTS o--N=N 2,544,936 Petitcolas etal Mar. 13, 1951 ll 20 2,883,373 BOssard et a1 Apr. 21, 1959 N FOREIGNPATENTS -OONHQ0CH3 981,432 France May 25, 1951 1 I 7. The complex cobaltcompound of the azo-dyestufr 1 l l

1. THE COMPLEX METAL COMPOUNDS SELECTED FROM THE GROUP CONSISTING OFCOBALT, COPPER AND NICKEL COMPOUNDS OF WATER-INSOLUBLE AZO-DYESTUFFS OFTHE FOLLOWING GENERAL FORMULA